3-(hydroxy lower alkyl)-aminomethyl-4-hydroxycoumarin compounds



li-(HYDROXY LGWER ALKYL)-AMINOMETHYL-4- HYDRGXYCUUMARIN COMPOUNDS Alice Uta Robertson and Dale N. Robertson, Madison,

and Karl Paul Link, Middleton, Wis., assignors to Wisconsin Alumni Research Foundation, Madison, Wis., a corporation of Wisconsin No Drawing. Application October 21, 1953, Serial No. 387,546

5 Claims. (Cl. 260-343.2)

The present invention relates to 3-substituted-4-hydroxycoumarin compounds. More specifically the invention is directed to 4-hydroxycoumarins substituted in the 3-position by the following group:

B-OH

where R represents a lower alkyl group. The following examples will serve to illustrate the invention.

EXAMPLE I 3-(u,u-dimethylethanol)-aminomethyl-4- hydroxycoumarin To a solution of 2.67 g. of 2-amino-2-methylpropanol-1 in 15 ml. of absolute ethanol is first added 1.62 g. of aqueous formalin (37% formaldehyde). To this solution is next added 3.72 g. of 4-hydroxycoumarin in 15 ml. of absolute ethanol. The resulting reaction mixture is warmed on a steam bath for a few minutes and then allowed to stand. The desired product which separates as a precipitate is recovered by filtration. It has a melting point of 183186 C. ((1).

EXAMPLE II 3- (Z-hydroxypropyl)-aminmethyl-4- hydroxycaumarin This product is prepared in accordance with Example I, by reacting l-amino-propanol-Z, formaldehyde and 4- hydroxycoumarin in equimolar amounts. It has a melting point of 192 C. (d).

2,779,768 Patented Jan. 29, 1957 2 EXAMPLE n1 3- (p-hydroxyethyl) -aminomethyl-4-hydr0xyc0umarin This product is prepared in accordance with the above 5 examples by employing as the amine, ethanolamine. It

has a melting point of 177 C. (d). In a similar manner other 3 hydroxy R aminomethyl-4-hydroxycoumarin compounds can be prepared by use of hydroxy-R-amines, where R stands for a lower alkyl group.

EXAMPLE 1V 3-allyl-aminomethyl-4-hydroxycoumarin where R represents a lower alkyl group.

2. The product, 3-(a,u-dimethylethanol)-aminomethy1- 4-hydroxycoumarin.

3. The product, 3-(2-hydroxypropyl)-aminomethyl-4 hydroxycoumarin.

4. The product, 3-(p-hydroxyethyl)-aminomethyl-4- hydroxycoumarin.

5. The product, 3 allyl aminomethyl 4 hydroxycoumarin.

References Cited in the file of this patent 0 UNITED STATES PATENTS 2,600,375 Ackermann June 17, 1952 2,610,152 Ackermann Sept. 9, 1952 2,680,747 Williams et al. June 8, 1954 5 OTHER REFERENCES Clinton et al.: J. A. C. S., 71, 3602-3606 (1949).

Boekelheide et al.: J. A. C. 8., vol. 72, pp. 5005-5009 (1950).

Arndt et al.: Berichte, vol. 84, p. 1322 (1951). 

1. A 4-HYDROXYCOUMARIN HAVING A SUBSTITUENT AT THE 3-POSITION REPRESENTED BY THE FOLLOWING FORMULA 